CN107803219B - Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application - Google Patents

Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application Download PDF

Info

Publication number
CN107803219B
CN107803219B CN201711135317.6A CN201711135317A CN107803219B CN 107803219 B CN107803219 B CN 107803219B CN 201711135317 A CN201711135317 A CN 201711135317A CN 107803219 B CN107803219 B CN 107803219B
Authority
CN
China
Prior art keywords
catalyst
nio
mno
carrier
zno
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711135317.6A
Other languages
Chinese (zh)
Other versions
CN107803219A (en
Inventor
谭猗生
杨国辉
张涛
宋法恩
解红娟
潘俊轩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanxi Institute of Coal Chemistry of CAS
Original Assignee
Shanxi Institute of Coal Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanxi Institute of Coal Chemistry of CAS filed Critical Shanxi Institute of Coal Chemistry of CAS
Priority to CN201711135317.6A priority Critical patent/CN107803219B/en
Publication of CN107803219A publication Critical patent/CN107803219A/en
Application granted granted Critical
Publication of CN107803219B publication Critical patent/CN107803219B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0425—Catalysts; their physical properties
    • C07C1/043—Catalysts; their physical properties characterised by the composition
    • C07C1/0435—Catalysts; their physical properties characterised by the composition containing a metal of group 8 or a compound thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
    • C07C2529/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/82—Phosphates
    • C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
    • C07C2529/85—Silicoaluminophosphates (SAPO compounds)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A catalyst for directly preparing low-carbon olefin from synthetic gas is prepared from active components ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O and a carrier, wherein the weight percentage of the carrier is as follows: ZnO: 30-60, MnO: 0.5 to 5, In2O3：0.5～5，Ga2O3：0.5～5，NiO：0.5～5，Cr2O3：10～45，K2O: 2-7, carrier: 10 to 40. The invention has the advantages of simple preparation method, high selectivity of low-carbon olefin and CO2Low selectivity and low methane selectivity.

Description

Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application
Technical Field
The invention relates to a catalyst for synthesizing low-carbon olefin, a preparation method and application thereof. In particular to a catalyst for directly synthesizing low-carbon olefin by synthesis gas, a preparation method and application thereof.
Background
Low carbon olefin (C2)＝～C4＝) Is a basic raw material for chemical industry. At present, the low-carbon olefin is obtained by adopting a steam cracking process in an ethylene combined device at home and abroad. The cracking device has high energy consumption and completely depends on petroleum resources. The technological route for developing the coal-based low-carbon olefin can reduce the dependence on petroleum resources and ensure the national energy safety by combining the energy structure characteristics of lean oil, less gas and rich coal in China. Coal-based low carbonMethods for the synthesis of carbon olefins include indirect and direct methods. The indirect method is to prepare methanol and dimethyl ether from coal, and then prepare olefin (MTO) from methanol and prepare low-carbon olefin (DMTO) from dimethyl ether. The direct method is a process for synthesizing low-carbon olefin by synthesis gas through a Fischer-Tropsch (FTO) path and a methanol synthesis path. Compared with indirect methods, the direct method has the advantages of short flow, low energy consumption, stronger competitiveness and better development prospect.
The fischer-tropsch pathway (FTO) is mainly composed of Fe-based catalysts, Co-based catalysts:
chinese patent CN104549343A discloses the preparation of catalyst by dipping and precipitating Fe, Cu, Zn, Cr, Mo and K on a silicon oxide and/or aluminum oxide catalyst at 280 ℃ of 220--1Under the reaction conditions of (1), the CO conversion rate is more than 80 percent, and C2-C4The selectivity of olefin is less than or equal to 67.6 percent. CN105709772A discloses a catalyst for preparing low-carbon olefin from high-activity stable supported iron-based synthesis gas and a preparation method thereof. The inner and outer surfaces of the alumina carrier are modified by the nitrogen-containing organic compound, so that the carbon chain growth and hydrogenation saturation of the low-carbon olefin are inhibited while the activity is improved. Conversion of CO>51 percent and the selectivity of the low-carbon olefin is less than 75 percent. CN105709768A discloses a preparation method of a catalyst for preparing low-carbon olefins from synthesis gas, which comprises the following steps: firstly, saturating an alumina carrier with the same volume to soak a buffer solution containing ammonium salt, drying until the adsorption capacity of the buffer solution containing ammonium salt is 30-60% of the saturated adsorption capacity of the alumina carrier, and then aging, drying and roasting to obtain the alumina carrier. Then, the zinc salt solution is dipped by adopting an unsaturated dipping method, dried and roasted. And then, impregnating the roasted carrier with a wetting liquid containing an adsorbent by adopting an unsaturated impregnation method. Obtaining the carrier containing the adsorbent. Then dipping the solution containing active metal iron and auxiliary agent manganese, drying and roasting to obtain the low-carbon olefin catalyst prepared from the synthesis gas. The CO conversion rate is more than 50 percent, and the selectivity of the low-carbon olefin is less than 70 percent. CN104549354A discloses a preparation method of an iron-based nano catalyst for preparing low-carbon olefin from synthesis gas. When the catalyst is prepared, the precursor of iron is dipped on the carbon material which is oxidized by potassium permanganate solution, and the carbon material is aged after the dipping is finishedDrying, and then roasting the reduced iron-based nano catalyst at high temperature. The carbon carrier comprises amorphous carbon, carbon black, mesoporous carbon, carbon nano tubes, nano carbon fibers and graphene, the hydrocarbon selectivity is 65.7 percent (% C), and C in hydrocarbon distribution2 ＝～C4 ＝To reach (50% C).
CN 105080597 a discloses a core-shell type catalyst with a silica or alumina supported Fe or Co catalyst as a core and ZSM-5 as a shell. H at 250-350 deg.C and 0.5-2.5MPa2/CO＝0.5～3， 1000～4000h-1Under the condition of (1), the CO conversion rate is higher than 80%, and the weight selectivity of C2-C4 olefin is less than or equal to 75%. Chinese patent 201510976381.1 discloses a core-shell catalyst for preparing low-carbon olefin from synthesis gas. The core of the composite material is FeMn with a certain proportion, and the shell is silicon oxide obtained by a hydrothermal synthesis method. CO conversion 45.32%, in hydrocarbon distribution, C2 ＝～C4 ＝63.17(wt.) percent is achieved.
Researches of high research institute of Shanghai of Chinese academy, Sunpuren et al show that the nanoprism structure of CoC can catalyze synthesis gas to synthesize low-carbon olefin with high selectivity (Nature, 2016,538 and 84). The evaluation in the fixed bed reactor showed that the conversion of CO was 20%, and the CO in the product was2Has a selectivity of 45%, C in the hydrocarbon product distribution2 ＝-C4 ＝Up to 60% of the total weight of the catalyst, and very high values of the alkylene ratio can be achieved over this catalyst.
Via the methanol route is also a viable alternative to the fischer-tropsch route. The Fischer-Tropsch synthesis route has a large amount of C in addition to obtaining a large amount of olefins5 +Hydrocarbons, the product distribution is wide, which causes difficulties in subsequent separation. Therefore, many researchers at home and abroad work on the aspect of synthesizing low-carbon olefin by a non-Fischer-Tropsch route. The Wang Ye professor of Xiamen university physically mixes ZnZr binary oxide and SAPO-34 molecular sieve, and when reacting at 400 ℃, the conversion rate of CO is about 10 percent, and C is2 ＝-C4 ＝The selectivity of the catalyst is as high as about 70 percent, the catalyst can continuously run for 100 hours, but CO in the product2The selectivity amounted to 50% (Ang)Aim, int.ed.,2016,55,4725-4728) of Chinese academy of sciences, university of chemical and physical research package letter and researcher team ZnCrAlOx methanol synthesis catalyst and SAPO-34 are compounded for research on preparation of low-carbon olefin from synthesis gas, and the compound catalyst is found to have CO conversion rate up to 17 percent and C in hydrocarbon2 ＝-C4 ＝Selectivity of up to 80%, C2-C4The total selectivity to hydrocarbons is as high as 94%, but approximately 45% of the CO is still present on this catalyst2(Science，2016,351,6277,1065-1068)。
The above research results show that the main problems in the existing catalyst systems are: although C in the hydrocarbon product distribution2 ＝～C4 ＝The selectivity of (A) is improved, but CO in the total product2The selectivity is higher and reaches 45 percent, which not only causes the waste of carbon resources, but also causes a large amount of CO2The formation of (b) causes serious ecological stress.
Disclosure of Invention
The invention aims to provide a preparation method which is simple, has high selectivity of low-carbon olefin and CO2The catalyst for directly synthesizing low-carbon olefin from synthesis gas with low selectivity and methane selectivity, and the preparation method and the application thereof.
The catalyst of the invention consists of active components of ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O and a carrier, wherein the weight percentage of the carrier is as follows:
ZnO：30～60，MnO：0.5～5，In2O3：0.5～5，Ga2O3：0.5～5，NiO：0.5～ 5，Cr2O3：10～45，K2o: 2-7, carrier: 10 to 40.
The support as described above is SAPO-34, HZSM-5 or SSZ-13.
The catalyst of the invention is prepared by a mixing and grinding method. Weighing ZnO, MnO and In proportion2O3、Ga2O3、NiO、 Cr2O3、K2O and a carrier, and grinding and mixing the mixture in a mortar for 0.5 to 3 hours, and then grinding and mixing the mixture for 0.2 hourHeating to the roasting temperature of 350-500 ℃ at the speed of-3 ℃ per min, and keeping the temperature for 10-20 hours at the roasting temperature to obtain the catalyst.
The catalyst of the invention is applied as follows:
and (3) catalyst reduction: with H2/(H2+N2) Diluting hydrogen with the molar ratio of 0.5-1 to serve as reducing gas, and keeping the gas space velocity for 50-200 h-1And reducing the catalyst for 3-10 hours under the conditions that the reduction pressure is 1-2 MPa and the reduction temperature is 350-400 ℃.
And (3) catalyst reaction: reduced catalyst in H2The mol ratio of/CO is 1.5-3.5, the reaction pressure is 2-8 MPa, the reaction temperature is 380-420 ℃, and the volume space velocity is 5000-11000 h-1Synthesizing lower olefins under the conditions of (1).
The invention prepares the catalyst by a mixing and grinding method. Compared with the existing catalyst, the catalyst has the advantages that: the commercial finished product is used as a catalyst preparation raw material, the catalyst preparation process is simple and convenient, and no pollutants such as waste water, waste gas and the like are discharged; by-product CO2The selectivity is low (less than 10 percent), and the utilization rate of carbon resources is high; the hydrocarbon has high distribution of medium-low carbon olefin (70-85%) and low distribution of methane (less than 10%).
Detailed Description
Example 1
9g of ZnO, 0.1g of MnO and 0.1g of In were weighed out2O3、0.7g Ga2O3、0.7g NiO、1.8g Cr2O3、 1g K2O and 2g SAPO-34 are put into a mortar to be ground and mixed for 0.5 hour, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 0.2 DEG/min and is kept for 15 hours at the roasting temperature to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, SAPO-34 wt.% of catalyst with composition (wt.%) of 58.44, 0.65, 4.55, 11.69, 6.49, 12.99.
With H2/(H2+N2) Diluting hydrogen with a molar ratio of 0.5 to be reducing gas at a space velocity of the reducing gas of 50h-1Reducing the catalyst for 5 hours under the conditions of reducing pressure of 2MPa and reducing temperature of 400 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 1.5, 2MPa, 420 ℃ and 8000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 15.6 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 8.5, 3.7, 87.8, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 6.5, 84.3, 6.8, 2.4.
Example 2
9g of ZnO, 0.7g of MnO and 0.7g of In were weighed out2O3、0.1g Ga2O3、0.1g NiO、1.8g Cr2O3、 1g K2O and 2g of HZSM-5 are put into a mortar to be ground and mixed for 3 hours, then the mixture is heated to 350 ℃ In a muffle furnace at the speed of 3 ℃/min and is kept at the roasting temperature for 20 hours to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, HZSM-5 wt.% catalyst with composition (wt.%) of 58.44, 4.55, 0.65, 11.69, 6.49, 12.99.
With H2/(H2+N2) Diluting hydrogen with a molar ratio of 0.5 to be reducing gas at a space velocity of 200h-1And reducing the catalyst for 10 hours under the conditions of the reduction pressure of 1MPa and the reduction temperature of 350 ℃.
Reduced catalyst in H2The mol ratio of/CO is 1.5, 8MPa, 380 ℃ and 11000h-1Synthesizing lower olefins under the conditions of (1). CO conversion ═ 17.9 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 6.7, 4.9, 88.4, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 6.3, 82.3, 8.5 and 2.9.
Example 3
9g of ZnO, 0.4g of MnO and 0.4g of In were weighed out2O3、0.4g Ga2O3、0.4g NiO、1.8g Cr2O3、 1g K2O and 2g SAPO-34 are put into a mortar for grinding and mixing for 2 hours, then the temperature is raised to 400 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute, and the mixture is kept for 10 hours at the roasting temperature to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, SAPO-34 weight percent (wt.%) of catalyst having a composition of 58.44, 2.6, 11.69, 6.49, 12.99.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 1 is used as reducing gas, and the space velocity of the reducing gas is 100h-1Reducing the catalyst for 10 hours under the conditions of reducing pressure of 2MPa and reducing temperature of 380 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 3.5, 6MPa, 400 ℃ and 5000h-1Synthesizing lower olefins under the conditions of (1). CO conversion ═ 34.1 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 5.8, 2.3, 91.9, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 9.8, 71.3, 17.7, 1.2.
Example 4
Weighing 8g ZnO, 0.4g MnO, 0.4g In2O3、0.4g Ga2O3、0.4g NiO、1.7g Cr2O3、 0.4g K2O and 2g of HZSM-5 are put into a mortar and mixed for 3 hours, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute, and the mixture is kept for 15 hours at the roasting temperature to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, HZSM-5 weight percent (wt.%) of catalyst 58.39, 2.92, 12.41, 2.92, 14.6.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 1 is used as reducing gas, and the space velocity of the reducing gas is 100h-1Reducing the catalyst for 3 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 400 ℃.
After reduction of catalystAgent of formula H2The mol ratio of the carbon dioxide to the CO is 3.5, 7MPa, 380 ℃ and 8000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 28.3 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) 4.6, 3.3, 92.1, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 8.4, 75.3, 14.5, 1.8.
Example 5
5g of ZnO, 0.4g of MnO and 0.4g of In were weighed out2O3、0.4g Ga2O3、0.4g NiO、1.8g Cr2O3、 0.4g K2O and 5.8g SAPO-34 are put into a mortar to be ground and mixed for 3 hours, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute and is kept for 10 hours at the roasting temperature to prepare ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O, SAPO-34 weight percent (wt.%) of 34.25, 2.74, 12.33, 2.74, 39.73.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 0.8 is used as reducing gas, and the space velocity of the reducing gas is 100h-1Reducing the catalyst for 8 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 380 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 6MPa, 390 ℃ and 6000h-1Synthesizing lower olefins under the conditions of (1). CO conversion was 32.7 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 7.2, 1.8, 91, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 7.9, 80.6, 9.4, 2.1.
Example 6
5g of ZnO, 0.4g of MnO and 0.4g of In were weighed out2O3、0.4g Ga2O3、0.4g NiO、1.8g Cr2O3、 0.4g K2O and 3.4g SAPO-34 are put into a mortar to be ground and mixed for 3 hours, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute and is kept for 20 hours at the roasting temperature to prepare ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O, SAPO-34 weight percent (wt.%) of catalyst 40.98, 3.28, 14.75, 3.28, 27.87.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 0.7 is used as reducing gas, and the space velocity of the reducing gas is 150h-1Reducing the catalyst for 5 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 380 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 5MPa, 400 ℃ and 5000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 20.6 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 8.9, 4.1, 87, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 9.1, 78.1, 11.2, 1.6.
Example 7
5g of ZnO, 0.4g of MnO and 0.4g of In were weighed out2O3、0.4g Ga2O3、0.4g NiO、4g Cr2O3、0.4g K2O and 3.4g HZSM-5 are put into a mortar and mixed for 2 hours, then the mixture is heated to 500 ℃ In a muffle furnace at the speed of 1.5 DEG/min and is kept for 20 hours at the roasting temperature to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, HZSM-5 weight percent (wt.%) of a catalyst having a composition of 34.72, 2.78, 27.78, 2.78, 23.61.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 0.6 is used as reducing gas, and the space velocity of the reducing gas is 150h-1Reducing the catalyst for 8 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 380 ℃.
Reduced catalystIn H2The mol ratio of the carbon dioxide to the carbon dioxide is 2.5, 5MPa, 410 ℃ and 7000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 22.3 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 7.5, 3.6, 88.9, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 5.9, 75.6, 15.9, 2.6.
Example 8
Weighing 7.8g ZnO, 0.4g MnO, 0.4g In2O3、0.4g Ga2O3、0.4g NiO、4g Cr2O3、 0.4g K2O and 3.4g SAPO-34 are put into a mortar to be ground and mixed for 2 hours, then the mixture is heated to 450 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute, and the mixture is kept at the roasting temperature for 18 hours to prepare ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O, SAPO-34 weight percent (wt.%) of catalyst 45.35, 2.33, 23.26, 2.33, 19.77.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 0.8 is used as reducing gas, and the space velocity of the reducing gas is 180h-1Reducing the catalyst for 5 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 390 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 5MPa, 380 ℃ and 10000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 16.1 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 6.7, 4.3, 89, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 3.5, 83.7, 11, 1.8.
Example 9
6g of ZnO, 0.2g of MnO and 0.2g of In were weighed out2O3、0.2g Ga2O3、0.2g NiO、8g Cr2O3、 0.4g K2O、3.4g SAPO-34, put into a mortar for grinding and mixing for 2 hours, then heated to 400 ℃ In a muffle furnace at the speed of 1.5 ℃ per minute, and kept at the roasting temperature for 18 hours to prepare ZnO, MnO and In2O3、Ga2O3、NiO、Cr2O3、K2O, SAPO-34 weight percent (wt.%) of catalyst having a composition of 32.26, 1.08, 43.01, 2.15, 18.28.
With H2/(H2+N2) The diluted hydrogen with the molar ratio of 0.8 is used as reducing gas, and the space velocity of the reducing gas is 170h-1And reducing the catalyst for 6 hours under the conditions of the reduction pressure of 1.5MPa and the reduction temperature of 390 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 3MPa, 400 ℃ and 9000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 25.6 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 7.9, 2.4, 89.7, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 7.1, 79.5, 11.1, 2.3.
Example 10
6g of ZnO, 0.2g of MnO and 0.2g of In were weighed out2O3、0.2g Ga2O3、0.2g NiO、8g Cr2O3、0.8g K2O and 3.4g SAPO-34 are put into a mortar to be ground and mixed for 2 hours, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 2 ℃ per minute and is kept at the roasting temperature for 20 hours to prepare ZnO, MnO and In2O3、 Ga2O3、NiO、Cr2O3、K2O, SAPO-34 wt.% of a catalyst having a composition (wt.%) of 31.58, 1.05, 42.11, 4.21, 17.89.
With H2/(H2+N2) The diluent gas with the molar ratio of 0.8 is the reducing gas, and the space velocity of the reducing gas is 150h-1Reducing the catalyst for 5 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 380 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 5MPa, 390 ℃ and 8000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 23.1 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 6.5, 3.1, 90.4, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 6.2, 80.2, 9.9, 3.7.
Example 11
6g of ZnO, 0.2g of MnO and 0.2g of In were weighed out2O3、0.2g Ga2O3、0.2g NiO、8g Cr2O3、0.8g K2O and 3.4g SSZ-13 are put into a mortar and ground for 2 hours, then the mixture is heated to 400 ℃ In a muffle furnace at the speed of 2 DEG/min and is kept at the roasting temperature for 20 hours to prepare ZnO, MnO and In2O3、Ga2O3、 NiO、Cr2O3、K2O, SSZ-13 wt.% catalyst with composition (wt.%) of 31.58, 1.05, 42.11, 4.21, 17.89.
With H2/(H2+N2) The diluent gas with the molar ratio of 0.8 is the reducing gas, and the space velocity of the reducing gas is 150h-1Reducing the catalyst for 5 hours under the conditions of reducing pressure of 1.5MPa and reducing temperature of 380 ℃.
Reduced catalyst in H2The mol ratio of the carbon dioxide to the CO is 2.5, 5MPa, 390 ℃ and 8000h-1Synthesizing lower olefins under the conditions of (1). CO conversion 20.5 (Cmol%); CO 22Oxygenate, hydrocarbon product selectivities (Cmol%) are 5.6, 1.2, 93.2, respectively; hydrocarbons such as methane and C2 ＝～C4 ＝、C2 0～C4 0The distribution of other hydrocarbons is (wt.%): 4.2, 85.3, 6.3 and 4.2.
The applicant further states that the present invention is illustrated by the above examples, but the present invention is not limited to the above embodiments, and all the ways of achieving the objects of the present invention by using methods similar to the present invention are within the scope of the present invention. It should be understood by those skilled in the art that any modifications to the present invention, the implementation of alternative equivalent substitutions and additions of steps, the selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (2)

1. A catalyst for preparing low-carbon olefin directly from synthetic gas is prepared from ZnO, MnO and In as active components2O3、Ga2O3、NiO、Cr2O3、K2O and a carrier, wherein the weight percentage of the carrier is as follows:
ZnO：30～60，MnO：0.5～5，In2O3：0.5～5，Ga2O3：0.5～5，NiO：0.5～5，Cr2O3：10～45，K2o: 2-7, carrier: 10-40;
the carrier is SAPO-34, HZSM-5 or SSZ-13;
the preparation method of the catalyst comprises the following steps:
weighing ZnO, MnO and In according to the composition of the catalyst2O3、Ga2O3、NiO、Cr2O3、K2And placing the O and the carrier into a mortar for grinding and mixing for 0.5-3 hours, then heating to the roasting temperature of 350-500 ℃ at the speed of 0.2-3 ℃/min, and keeping the temperature for 10-20 hours at the roasting temperature to obtain the catalyst.
2. The application of the catalyst of claim 1 in the preparation of light olefins directly from synthesis gas, comprising the steps of:
and (3) catalyst reduction: with H2/（H2+N2) Diluted hydrogen with the molar ratio = 0.5-1 is used as reducing gas, and the air speed is 50-200 h-1Reducing the catalyst for 3-10 h under the conditions that the reduction pressure is 1-2 MPa and the reduction temperature is 350-400 ℃;
and (3) catalyst reaction: reduced catalyst in H2The mol ratio of/CO is 1.5-3.5, the reaction pressure is 2-8 MPa, the reaction temperature is 380-420 ℃, and the volume isThe airspeed is 5000 ~ 11000h-1Synthesizing lower olefins under the conditions of (1).
CN201711135317.6A 2017-11-16 2017-11-16 Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application Active CN107803219B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711135317.6A CN107803219B (en) 2017-11-16 2017-11-16 Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711135317.6A CN107803219B (en) 2017-11-16 2017-11-16 Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application

Publications (2)

Publication Number Publication Date
CN107803219A CN107803219A (en) 2018-03-16
CN107803219B true CN107803219B (en) 2021-03-02

Family

ID=61580347

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711135317.6A Active CN107803219B (en) 2017-11-16 2017-11-16 Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application

Country Status (1)

Country Link
CN (1) CN107803219B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111068640B (en) * 2018-10-18 2024-03-26 中国石油化工股份有限公司 Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparing low-carbon olefin from synthesis gas
CN109433252B (en) * 2018-11-30 2022-01-07 大连理工大学 CO (carbon monoxide)2Oxide C2H6Dehydrogenation to C2H4And a process for preparing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6638892B1 (en) * 2002-04-18 2003-10-28 Conocophillips Company Syngas conversion and catalyst system employed therefor
CN103521259A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparation of olefine from synthesis gas and preparation method thereof
CN106311317A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst and method for directly preparing light olefins from synthesis gas by one-step process
WO2017074558A1 (en) * 2015-10-30 2017-05-04 Dow Global Technologies Llc Process to convert synthesis gas to olefins over a bifunctional chromium oxide/zinc oxide-sapo-34 catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6638892B1 (en) * 2002-04-18 2003-10-28 Conocophillips Company Syngas conversion and catalyst system employed therefor
CN103521259A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparation of olefine from synthesis gas and preparation method thereof
CN106311317A (en) * 2015-07-02 2017-01-11 中国科学院大连化学物理研究所 Catalyst and method for directly preparing light olefins from synthesis gas by one-step process
WO2017074558A1 (en) * 2015-10-30 2017-05-04 Dow Global Technologies Llc Process to convert synthesis gas to olefins over a bifunctional chromium oxide/zinc oxide-sapo-34 catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Conversion of Synthesis Gas to Light Olefins: Impact of Hydrogenation Activity of Methanol Synthesis Catalyst on the Hybrid Process Selectivity over Cr−Zn and Cu−Zn with SAPO-34";Alexey V. Kirilin et al.;《Industrial & Engineering Chemistry Research》;20170921;第56卷;第13392-13401页 *

Also Published As

Publication number Publication date
CN107803219A (en) 2018-03-16

Similar Documents

Publication Publication Date Title
CN108568313B (en) Catalyst and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation
CN102234212B (en) Method for directly converting synthetic gas into low-carbon olefins
CN109939728A (en) A kind of method that supported catalyst and synthesis gas directly convert producing light olefins
CN109939667A (en) A kind of method that catalyst and synthesis gas directly convert producing light olefins
CN109745965B (en) Catalyst containing CeZr oxide and method for preparing low-carbon olefin by directly converting carbon monoxide through hydrogenation
KR100993452B1 (en) Process for producing olefin by catalytic cracking of hydrocarbon
CN105536811A (en) A core-shell type catalyst for lower-alkene preparation from synthetic gas, a preparing method thereof and applications of the catalyst
CN108970600A (en) A kind of method that catalyst and synthesis gas directly convert producing light olefins
CN114939433A (en) Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof
CN105983435B (en) A kind of isomerization of butene catalyst and its preparation method and application
CN108940355B (en) Alkali modified catalyst and method for preparing ethylene through carbon monoxide hydrogenation reaction
CN111375444A (en) Core-shell iron-based catalyst for directly producing aromatic hydrocarbon from synthesis gas and preparation method and application thereof
CN107803219B (en) Catalyst for directly preparing low-carbon olefin from synthesis gas, preparation method and application
CN107243347A (en) A kind of ferrum-based catalyst of synthesis gas alkene and its production and use
CN109939723A (en) A kind of method that catalyst and synthesis gas directly convert ethylene processed
CN105435801B (en) Load typed iron catalyst and its preparation method and application
CN107029783B (en) A kind of LPG is converted into the catalyst and preparation method thereof of ethylene, propylene
CN109939722A (en) A kind of method of organic base-modified composite catalyst and co hydrogenation ethylene
CN109647492B (en) Catalyst for directly producing low-carbon olefin by synthesis gas
CN103831128B (en) A kind of modified nano molecular sieve hydroaromatization catalyst and preparation method
CN112246275A (en) Catalyst for preparing olefin by oxidizing low-carbon alkane with carbon dioxide and preparation method thereof
CN109939669A (en) A kind of method of base-modified composite catalyst and carbon monoxide hydrogenation ethylene
CN109939668A (en) A method of the B acid catalyst of type containing LF and synthesis gas directly convert ethylene processed
CN114471744B (en) Pretreatment method of iron-based catalyst and application thereof
JP4159853B2 (en) Catalyst for catalytic cracking of hydrocarbon and catalytic cracking method using the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant